Treatment and after-treatment of metal with carbohydrate-modified polyphenol compounds

ABSTRACT

A metal treatment solution comprising an effective amount of a soluble or dispersible compound which is a derivative of a polyphenol. Novel derivatives of polyphenol compounds useful in the treatment of the surface of metal articles is provided. Novel surface treatment solutions or dispersions, and methods for using these solutions is provided. Carbohydrate-modified polyphenol compounds are utilized in the present invention. The molecular weight of the polyphenols used in the preparation of derivatives of the present invention are in the range of about 360 to about 30,000 or greater. The resulting derivatives will typically have a molecular weight of up to about 2,000,000 with molecular weights within the range of about 700 to about 70,000 being preferred.

BACKGROUND AND SUMMARY OF INVENTION

The present relates to the field of protective and/or decorative surfacetreatment of articles, particularly metals, plastics, and the like.

The present invention comprises novel derivatives of polyphenolcompounds useful in the treatment of the surface of metal articles. Thepresent invention also encompasses novel surface treatment solutions ordispersions, and methods of using these solutions or dispersions.

In accordance with the present invention, novel compositions, solutionsand dispersions, and methods are provided for use in providing aprotective or decorative metal surface treatment; these include thetreatment of previously untreated bare metal surfaces, thepost-treatment of phosphatized or conversion coated metal surfaces, theapplication of a paint or other decorative coating or film, and thelike. The present invention additionally includes compositions andmethods that are particularly useful for treating various metal surfacesincluding aluminum, steel and zinc metal surfaces. The compositions,solutions and dispersions, and methods of the present invention providea coating on the metal surface which is effective in enhancing thecorrosion resistance and paint adhesion characteristics of the metalsurface whether previously conversion coated or not. A further and moredetailed understanding of this invention can be obtained from thefollowing disclosure. All parts and percentages are by weight unlessotherwise indicated.

The need for applying protective coatings to metal surfaces for improvedcorrosion resistance and paint adhesion characteristics is well known inthe metal finishing art as well as in other metal arts. Traditionally,metal surfaces are treated with chemicals which form a metal phosphateand/or metal oxide conversion coating on the metal surface to improvethe corrosion resistance and paint adhesion thereof. The conversioncoated metal surfaces are also generally rinsed or post-treated with asolution containing a hexavalent chromium compound for even greatercorrosion resistance and paint adhesion.

Because of the toxic nature of hexavalent chromium, expensive wastewatertreatment equipment must be employed to remove the residual chromatesfrom plant effluent to comply with environmental regulations and toimprove the quality of rivers, streams, and drinking water sources.Hence, although the corrosion resistance and paint adhesioncharacteristics of conversion coated metal surfaces can enhanced by anafter-treatment solution containing hexavalent chromium, thedisadvantages in recent years have lead to much research and developmentin an effort to uncover effective alternatives to the use ofpost-treatment solutions containing hexavalent chromium. One alternativeto the use hexavalent chromium involves the use of derivatives ofpolyphenol compounds such as poly-vinyl phenol. Suitable derivatives andsuitable treatment solutions are disclosed in the earlier U.S. Pat. No.4,517,028, May 14, 1985; U.S. Pat. No. 4,376,000, Mar. 8, 1983 toLindert; U.S. Pat. No. 4,433,015, Feb. 21, 1984 to Lindert; and U.S.Pat. No. 4,457,790, July 3, 1984 to Lindert, et al.; all of which areexpressly incorporated herein by reference. Also see the two commonlyassigned applications filed the same date herewith entitled "TreatmentAnd After-Treatment Of Metal With polyphenol Compounds", U.S. Ser. No.07/128672; and "Treatment And After-Treatment Of Metal With AmineOxide-Containing polyphenol Compounds", U.S. Ser. No. 07/128756; both ofwhich are expressly incorporated herein by reference.

Further, the art has also recognized that existing aluminum treatmentsystems suffer from many disadvantages.

The present relates to the use of novel derivatives of polyphenolcompounds for treatment of the surface of metal articles. In accordancewith the present invention, a novel composition and method are providedfor in metal treatment. These compositions and methods may be employedfor the treatment of previously untreated metal surfaces, particularlyaluminum, or for the post-treatment of phosphatized or conversion coatedmetal surfaces. The present invention additionally includes compositionsand methods for treating various metal surfaces including aluminum,steel and zinc metal surfaces. The compositions and methods of thepresent invention provide a coating on the metal surface which iseffective in enhancing the corrosion resistance and paint adhesioncharacteristics of the metal surface whether previously conversioncoated or not. A further and more detailed understanding of thisinvention can be obtained from the unless otherwise indicated.

DETAILED DESCRIPTION OF THE INVENTION

In a typical metal treatment operation employing a solution of thisinvention, the metal to be treated is initially cleaned by a chemical orphysical process to remove grease and dirt from the surface and thenwater rinsed. The metal surface is then brought into contact with thetreatment solution of this invention. Alternatively, instead ofcontacting the metal surface with the treatment solution of thisinvention immediately following the cleaning process, a conversioncoating solution is applied to or otherwise used to pre-treat the metalsurface in a conventional manner to form a conversion coating thereon.Then the conversion coated surface is water rinsed and the metal surfaceis brought into contact with the treatment solutions of the presentinvention.

Although solutions and/or dispersions of the invention can beeffectively applied to treated or untreated metal surfaces, speakinggenerally the present invention is particularly useful if the metalsurface has previously been conversion coated and the invention isaccordingly used as a post-treatment; accordingly, as used herein, theterm "post-treatment" means the treatment of a metal surface which isnot bare metal, and preferably has been previously treated With aconventional conversion coating process. Such conversion coatings arewell known and have been described, for example, in Metal Handbook,Volume II, 8th Edition, pp. 529-547 of the American Society for Metalsand in Metal Finishing Guidebook and Directory, pp. 590-603 (1972), thecontents of both of which are specifically incorporated by referenceherein.

The compositions and processes of the present invention are useful intreating a broad range of metal surfaces, including metals havingsurfaces that have been conversion coated with suitable conversioncoatings such as iron phosphate, manganese phosphate, zinc phosphate,zinc phosphate modified with calcium, nickel, or manganese ions.Examples of suitable metal surfaces include zinc, iron, aluminum andcold-rolled, polished, pickled, and hot-rolled steel and galvanizedsteel surfaces. As used herein, the term "metal surface" includes bothuntreated metal surfaces and conversion coated metal surfaces. Withregard to aluminum surfaces, the compositions and methods of the presentinvention can be applied prior to or in place of, any additionalcorrosion-resistance/paint-base surface treatments.

As used herein, the term "metal surface" includes both untreated metalsurfaces and conversion coated metal surfaces.

The treatment solution of the present invention comprises an effectiveamount of a soluble or dispersible treatment compound, frequentlyreferred to below as a polymer Material, in a liquid, preferablyaqueous, medium. The soluble or dispersible compound employed in thepresent invention is selected from the group consisting of any one ofthe following Polymer Materials a, b, c, d (characterized below), theirsalts, and mixtures thereof. Salts include the acid and alkaline saltsthereof.

In general, the compositions and method of the present invention aresimilar to those disclosed in my co-pending U.S. patent applicationentitled TREATMENT AND AFTER-TREATMENT OF METAL WITH POLYPHENOLCOMPOUNDS, Ser. No. 07/126872 filed herewith, and expressly incorporatedherein by reference. However, unlike those compositions and methods, atleast a portion of the final resin Polymer Material of the presentinvention must include a "Z" moiety and further, at least a portion ofsaid "Z" moiety must be modified by the inclusion of a polyhydroxyalkyl-amine functionality resulting from the condensation of an amine orNH₃ with a ketose, aldose, or other alkylaminopolyhydroxy compound,preferably having from about 3 to about 8 carbon atoms. Suchmodifications may also be made to polyphenolics other than thosedisclosed in my co-pending application, such as those polyphenolicderivatives described in my U.S. Pat. No. 4,376,000 issued Mar. 8, 1983;U.S. Pat. No. 4,443,015 issued Feb. 21, 1984; and U.S. Pat. No.4,517,028 issued May 14, 1985; all expressly incorporated herein byreference. In particular, the preferred materials of the presentinvention are based on certain aminosaccharide derivatives ofpolyphenolics which have been found useful in treating metal, especiallybare aluminum metal. A metal surface contacted with a treatment solutionof the present invention has enhanced corrosion resistance and paintadhesion characteristics. Further understanding of this invention willbe had from the following disclosure, wherein all parts and percentagesare by weight unless otherwise indicated.

The polyphenol compounds of the present inventions are polymer Materials(a)-(d) below, their salts, and mixtures thereof. The treatmentcompositions of the present invention comprise an effective amount of asoluble or dispersible treatment compound (Polymer Material) in acarrier that is suitable for surface treatment, i.e., one that allowsthe selected polymer Material to be deposited or otherwise placed on thesurface of, for example, a metal. The soluble or dispersible compoundemployed in the present invention is selected from the group consistingof any one of the following Polymer Materials (a)-(d) (characterizedbelow), solutions or dispersions of these Polymer Materials, theirsalts, and mixtures thereof. Salts include the acid and alkaline saltsthereof.

The methods of the present invention comprise contacting a metal surfacewith treatment compositions described herein.

Polymer Material (a)

In accordance with the present invention a polymer useful in metaltreatment applications is selected from polymer Materials (a)-(d).Polymer Material (a) comprises a polymer material having at least oneunit having the formula: ##STR1## where:

R₁ through R₃ are independently selected for each of said units from thegroup consisting of hydrogen, an alkyl group having from 1 to about 5carbon atoms, or an aryl group having about 6 to about 18 carbon atoms;

Y₁ through Y₄ are independently selected for each of said units from thegroup consisting of hydrogen, --CR₁₁ R₅ OR₆, --CH₂ Cl, or an alkyl oraryl group having from 1 to 18 carbon atoms, or Z; ##STR2## however, atleast a fraction of the Y₁, Y , Y₃ or Y₄ of the final compound ormaterial must be Z and at least a fraction of said Z must contain apolyhydroxy alkyl-amine functionality resulting from the condensation ofan amine or NH₃ and a ketose, aldose or other alkylaminopolyhydroxycompound having from about 3 to about 8 carbon atoms followed byreduction to an amine (from the imine);

R₅ through R₁₂ are independently selected for each of said units fromthe group consisting of hydrogen, an alkyl, aryl, hydroxy-alkyl,amino-alkyl, mercapto-alkyl, or phospho-alkyl moiety; R₁₂ can also be--O.sup.(-1) or --OH, in order to form an amine oxide or a hydroxylamine;

W₁ is independently selected for each of said units from the groupconsisting of hydrogen; an acyl moiety; an acetyl; a benzoyl moiety;3-allyloxy-2-hydroxy-propyl-; 3-benzyloxy-2-hydroxy-propyl-;3-alkylbenzyloxy-2-hydroxy-propyl-; 3-phenoxy-2-hydroxy-propyl-;3-alkylphenoxy-2-hydroxy-propyl-; 3-butoxy-2-hydroxy-propyl;3-alkyloxy-2-hydroxy-propyl; 2-hydroxyoctyl-; 2-hydroxy-alkyl-;2-hydroxy-2-phenyl ethyl-; 2-hydroxy-2-alkyl phenyl ethyl-; benzyl-;methyl-; ethyl-; propyl-; alkyl; allyl; alkyl benzyl-; haloalkyl-;haloalkenyl; 2-chloro-propenyl-; sodium, potassium; tetra aryl ammonium;tetra alkyl ammonium; tetra alkyl phosphonium; tetra aryl phosphonium;or a condensation product of ethylene oxide, propylene oxide, a mixture,or copolymer thereof;

Preferred final materials are based on a vinyl phenolic moiety or methylvinyl phenolic moiety. For example, vinyl phenol isopropenyl phenol andderivatives thereof may be used.

It will be appreciated that the depiction above represents a repeatingunit that characterizes the compound or materials of the presentinvention; no terminating end units are depicted. The end group notdepicted of the polymers of the present invention can be selected by theskilled artisan relying upon art-disclosed techniques. For example, theend groups of the polymer may either those resulting from the specificpolymerization process employed or those intentionally added to alterthe polymer characteristics. For example, the end groups may behydrogen, hydroxyl, initiation fragments, chain transfer agents,disproptionation groups, or other similar methods of terminating agrowing polymer chain.

Polymer Material (b)

Polymer Material (b) comprises a polymer material having at least oneunit having the formula: ##STR3## wherein:

R₁ through R₂ are independently selected for each of said units from thegroup consisting of hydrogen, an alkyl group having from 1 to about 5carbon atoms, or an aryl group having from about 6 to about 18 carbonatoms;

Y₁ through Y₃ are independently selected for each of said units from thegroup consisting of hydrogen, --CR₄ R₅ OR₆, --CH₂ Cl, an alkyl or arylgroup having from 1 to 18 carbon atoms, or Z, ##STR4## but at least afraction of the Y₁, Y₂, or Y₃ of the final compound must be Z, and atleast a fraction of said Z must contain a polyhydroxy alkyl-aminefunctionality resulting from the condensation of an amine or NH₃ and aketose, aldose or other alkylaminopolyhydroxy compound having from about3 to about 8 carbon atoms;

R₄ through R₁₂ are independently selected for each of said units fromthe group consisting of hydrogen, or an alkyl, aryl, hydroxy-alkyl,amino-alky, mercapto-alkyl or phospho-alkyl moiety; R₁₂ may also be--OH.sup.(-1) in order to form an amine oxide or a hydroxyl amine;

W₂ is independently selected for each of said units from the groupconsisting of hydrogen; an acyl moiety; acetyl; benzoyl;3-allyloxy-2-hydroxy-propyl-; 3-benzyloxy-2-hydroxy-propyl-;3-alkylbenzyloxy-2-hydroxy-propyl-; 3-phenoxy-2-hydroxy-propyl-;3-alkylphenoxy-2-hydroxy-propyl-; 3-butoxy-2-hydroxy-propyl-;3-alkyloxy-2-hydroxy-propyl-; 2-hydroxyoctyl-; 2-hydroxy-alkyl-;2-hydroxy-2-phenyl-ethyl-; 2-hydroxy-2-alkyl-phenylethyl-; benzyl-;methyl-; ethyl-; propyl-; alkyl; allyl-; alkylbenzyl-; haloalkyl-;haloalkenyl; 2-chloro-propenyl-; or a condensation product of ethyleneoxide, propylene oxide, a mixture, or copolymer thereof;

Polymer Material (c)

Polymer Material (c) comprises a co-polymer material wherein at leastone portion of said co-polymer has the structure: ##STR5##

and at least a fraction of said portion is polymerized with one or moremonomers having a C═C moiety. Useful include those independentlyselected for each of said units from the group consisting ofacrylonitrile, methacrylonitrile, methyl acrylate, methyl methacrylate,vinyl acetate, vinyl methyl ketone, isopropenyl methyl ketone, acrylicacid, methacrylic acid, acrylamide, methacrylamide, n-amyl methacrylate,styrene, m-bromostyrene, p-bromostyrene, pyridine,diallyldimethylammonium salts, 1,3-butadiene, n-butyl acrylate,tert-butylamino-ethyl methacrylate, n-butyl methacrylate, tert-butylmethacrylate, n-butyl vinyl ether, tert-butyl vinyl ether,m-chlorostyrene, o-chlorostyrene, p-chlorostyrene, n-decyl methacrylate,N,N-diallylmelamine, N,N-di-n-butylacrylamide, di-n-butyl itaconate,di-n-butyl maleate, diethylaminoethyl methacrylate, diethyleneglycolmonovinyl ether, diethyl fumarate, diethyl itaconate, diethylvinylphosphonate, vinylphosphonic acid, diisobutyl maleate, diisopropylitaconate, diisopropyl maleate, dimethyl fumarate, dimethyl itaconate,dimethyl maleate, di-n-nonyl fumarate, di-n-nonyl maleate, dioctylfumarate, di-n-octyl itaconate, di-n-propyl itaconate, n-dodecyl vinylether, ethyl acid fumarate, ethyl acid maleate, ethyl acrylate, ethylcinnamate, N-ethylethacrylamide, ethyl methacrylate, ethyl vinyl ether,5-ethyl-2-vinylpyridine, 5-ethyl-2-vinylpyridine 1-oxide, glycidylacrylate, glycidyl methacrylate, n-hexyl methacrylate, 2-hydroxyethylmethacrylate, 2-hydroxypropyl methacrylate, isobutyl methacrylate,isobutyl vinyl ether, isoprene, isopropyl methacrylate, isopropyl vinylether, itaconic acid, lauryl methacrylate, methacrylamide, methacrylicacid, methacrylonitrile, N-methylolacrylamide, N-methylolmethacrylamide,N-isobutoxymethylacrylamide, N-isobutoxymethylacrylamide,N-alkyloxymethylacrylamide, N-alkyloxymethylmethacrylamide,N-vinyl-caprolactam, methyl acrylate, N-methylmethacrylamide,α-methylstyrene m-methylstyrene, o-methylstyrene, p-methylstyrene,2-methyl-5-vinylpyridine, n-propyl methacrylate, sodiump-styrenesulfonate, stearyl methyacrylate, styrene, p-styrenesulfonicacid, p-styrenesulfonamide, vinyl bromide, 9-vinylcarbazole, vinylchloride, vinylidene chloride, 1-vinylnaphthalene, 2-vinylnaphthalene,2-vinylpyridine, 4-vinylpyridine, 2-vinylpyridine N-oxide,4-vinylpyrimidine, N-vinylpyrrolidone; and W₁, Y₁ -Y₄ and R₁ -₁₂ are asin (a), above.

Within such materials, the ratio of any single monomer to any othermonomer can be about 1:99 to about 99:1, preferably about about 5:1 toabout 1:5, and more preferably 1.5:1 to about 1:1.5.

Polymer Material (d)--Condensate polymers

By the term "condensation polymers" is meant the following:

A condensation polymer of polymer materials (a), (b), or (c), whereincondensable forms (i.e., modified as noted below) of (a), (b), or (c),or mixtures thereof, is condensed with a second compound selected fromthe group consisting of phenols (preferably phenol, alkylphenol,arylphenol, cresol, resorcinol catechol, pyrogallol), tannins, (bothhydrolyzable and condensed) novolak resins, lignin compounds, togetherwith aldehydes, ketones or mixtures thereof, to produce a condensationresin product, that is a prepolymer of Polymer Material (d). Thiscondensation resin prepolymer product is then further reacted by theaddition of "Z" to at least a portion of it by reacting said resinprepolymer product with an aldehyde or ketone and a secondary amineproducing a final adduct which can react with an acid and/or can bereacted with hydrogen peroxide to generate an amine oxide. The amineoxide can then be acid neutralized to form the hydroxyl amine ifdesired.

While this condensation product is described for convenience as beingprepared by a sequential reaction, it will be appreciated that thesematerials can be prepared by carrying out the necessary steps in anyorder, or simultaneously. However, the sequence described is preferred.

It is appreciated by those skilled in the art, that the alkenylphenolicmoieties of the present invention can be either randomly distributedwithin the copolymer and terpolymer or can be synthesized to constitutea block orientated polymer, depending upon the methods and conditionsused for polymerization.

Preferred aldoses, ketoses, and derivatives for use in the abovematerials include, without limitation, glucose, fructose, alditols suchas mannitol, aribanose, mannose, ribose, ribitol, and the like. Acidssuch as aldonic and aldaric acids may also be employed. Disaccharidesand polysaccharides that can be easily hydrolyzed under reactionconditions to one or more of the useful aldoses and ketoses may also beemployed.

The present invention further relates to the polymer metal treatmentsolutions comprising an effective amount of Polymer Material (a), (b),(c), (d) or mixtures thereof and to the process of treating a metalsurface by contacting the metal surface with metal treatment solution.The present invention is especially useful with respect to aluminummetal surfaces.

In a typical treatment operation employing a solution and process ofthis invention, the metal surface to be treated is initially cleaned bya chemical or physical process, and water rinsed to remove grease anddirt from the surface. The metal surface is then brought into contactwith the treatment solution of this invention, for example, by means ofa squeegee roller coater. The treated metal is then dried, for example,by flash drying in a 200° F. oven for 30 seconds.

The surface treatment solutions of this invention comprise PolymerMaterials (a), (b), (c), (d), or mixtures thereof (with or without therequirement that the Z moeity be present), are preferably dissolved ordispersed in a carrier suitable for depositing or otherwise placing thePolymer Material on the surface of a metal, i.e., as a metal surfacetreatment, metal surface post treatment, a paint, protective film, or asa component of any of the foregoing.

These Polymer Materials of the present invention may be made soluble ordispersible in water or organic solvent-type carriers. They maytherefore be employed as a treatment solution when dissolved in water orin an organic solvent such as, for example, ethanol. Preferably, thePolymer Material selected is used in aqueous solution as a carrier.

Accordingly, it is highly desirable to provide or improve the watersolubility or water dispersibility of the selected Polymer Material. Inaddition to employing the polyhydroxyalkyl-amine functionality, this ispreferably done with an acid used for neutralization and/or complexationof a "Z" moiety thereof. Such acids may be organic or inorganic. Usefuland preferred acids for this purpose carbonic acid, acetic acid, citricacid, oxalic acid, ascorbic acid, phenylphosphonic acid,chloromethylphosphonic acid; mono, di and trichloroacetic acid,trifluoroacetic acid, nitric acid, phosphoric acid, hydrofluoric acid,sulfuric acid, boric acid, hydrochloric acid, hexafluorosilicic acid,hexafluorotitanic acid, hexafluorozirconic acid, and the like; these maybe employed alone or in combination with each other and may beneutralized by conventional acid-base reactions or by complexing. In ahighly preferred embodiment, the addition of water to the neutralized,overneutralized or partially neutralized treatment compounds mentionedabove results in a water soluble or dispersible solution or emulsion ofthe polymer useful for metal treatment.

Alternately, the final Polymer Material/polyphenol compounds of thepresent invention can be made water soluble or dispersible byneutralization of the phenolic group with an organic or inorganic base.Suitable bases for this purpose include tetra-alkylammonium hydroxidessuch as tetrabutylammonium hydroxide, tetra arylammonium hydroxide,sodium hydroxide, potassium hydroxide and the like.

In a highly preferred embodiment, the final Polymer Material can beprepared such that the "Z" moiety does not require neutralization, i.e.,an amine oxide or the like.

The molecular weight of the polyphenols used in the preparation ofderivatives claimed in the present invention can be a dimer, but maypreferably be low molecular weight oligomers or resinous polymers havingmolecular weights in the range of about 360 to about 30,000 or greater.The upper limit of molecular weight of materials useful in surfacetreatment compositions is generally determined by the functionallimitation that the derivative therefrom must be soluble or dispersiblein the selected carrier. The resulting derivatives of the formulae setforth hereinabove will typically have a molecular weight of up to about2,000,000 with molecular weights within the range of about 700 to about70,000 being preferred.

Typically, the pH of the aqueous solution will vary from about 0.5 toabout 14. Generally the aqueous solution will have a pH of from about2.0 to about 12 both for the stability of the solution and for bestresults on the treated metal surfaces.

It is contemplated that the compositions and treatment solutions of thepresent invention can be used to treat the surface of a variety ofmaterials, particularly metal and plastic or "plastic-like" surfaces.Preferred metal surfaces include iron-, zinc- and aluminum-based metals.Preferred "plastic-like" material surfaces include resin or polymericmaterials, including thermoplastic and thermosetting materials, as wellas natural rubbers, mixtures of these materials, and the like.

The coating applied may be for protection or decorative in nature, ormay be a preparation of the surface for another treatment, it may alsoserve several functions at once.

The thickness of the final dry or cured coating will depend on itspurposes or functions, and may typically range from about 0.0001 mil toabout 25 mils or greater. The typical and preferred metal surfacetreatment (such as a conversion-type protective/paint base coating) isin the range of about 0.05 mil and below, and more preferably about0.0001 mil to about 0.05 mil. When acting as a paint or decorative andprotective surface treatment, the resulting coating thickness is about0.05 mil and above, preferably about 0.05 to about 25 mils, and morepreferably about 0.05 to about 10 mils.

It is further contemplated that the treatment compounds of the presentinvention will generally be used in surface treatment compositions overa wide range of concentrations. It will be appreciated that the levelsof useful or useful ranges will vary with many factors well-known to theskilled artisan. Useful levels of the compositions of the presentinvention dissolved or dispersed in a carrier may be in the range ofabout 0.001% to about 80 percent, depending upon the ultimate use. Forexample, when used as a pre- or post-treatment of a metal surface,useful levels typically include a dilute to moderate concentration offrom about 0.001% to about 20%, by weight, preferably about 0.001% toabout 10 percent, by weight, and still more preferably about 0.001% toabout 5% by weight. Practically speaking, a concentration of 0.0025 to1% is preferred in metal surface treatment (compositions especially foriron-, zinc-, or aluminum-based metal surfaces). However, under somecircumstances (for example when transporting or storing the solution orwhen using it in a "dry-in-place" system), a concentrate of the solutionmay be preferred. Higher levels (for example, as high as 80% by weight)may also be employed when the treatment composition is part of a paintsystem.

Of course, the treatment solutions of the present invention can alsocomprise ingredients typically found in other similar treatmentcompositions, (e.g., conversion coating compositions) in addition to thepolymer compound. For example, the treatment solution may optionallycomprise an effective amount of a treatment compound according to thepresent invention, and from about 0.001% to about 3.0% of a metal ion.Metal ions useful for metal treatment in combination with polyphenols ofthis invention include first row transition metals generally, GroupIV-B-metals generally, iron, nickel, cobalt, vanadium, chromium,titanium, zirconium hafnium, scandium, yttrium, lanthanum and theirrespective lanthanoid and Actinoid metals, as well as molybdenum andtungsten. In addition, tin, silicon, and aluminum compounds, and inparticular their oxides, in combination with the materials of thepresent invention can be used to improve both the effectiveness orperformance of the treatment solution in use. Such materials may alsoreduce the time of application of treatment solution to the metalsurface to as short a time as about 2 to 5 seconds as might be requiredon a coil coating line. Complex fluoride materials may also employed.For example, suitable complex fluoride materials include: BF₄.sup.(- 1),hexafluoride and the like.

It must be appreciated that the addition of metal ions may result in theformation of polymer-metal ion chelating compounds.

The Polymer Materials of the present invention may also be employed insurface treatment composition and surface treatment methods other thanthose described above. For example, the Polymer Material of the presentinvention may be empolyed as a component of a dry-in place system, apaint system, or as an additive in a system needing a crosslinkingagent.

For example, the Polymer Materials of the present invention may be usedin a film forming composition that includes a pigment, i.e. may be usedas a paint. They may also be employed as an additional component inconjunction with other polymeric materials in a paint system. Suchprotective, functional and/or decorative surface treatment solutionspreferably employ typical electrocoat/electrodeposition additives attheir art--established levels. The Polymer Materials of the presentinvention are particularly useful in cathodic electrocoat surfacetreatment compositions. The polymer materials of the present inventionmay be employed as a solubilizing polymer and/or binder in anelectrocoat paint. They may be so employed alone or in conjunction withother binder resins. For example, such paint compositions may optionallyinclude pigments (both organic and inorganic); film forming resins;binders such as epoxys, oils, alkyds, acrylics, vinyls, urethanes,phenolics, etc.; and solvents including hydrocarbons, chlorinatedaliphatics and aromatics, alcohols, ethers, ketones, esters; nitratedmaterials; and particulate zinc.

Further, the Mannich derivatives of the present invention when employedwith other binders will also act as a crosslinking agent to produce ahighly-crosslinking coating upon curing or drying of the film.Accordingly, it may be part of or all of the needed crosslinking system.

Accordingly, the compositions and materials of this invention can beused alone or in conjunction with other resins as polymeric coatings onsurfaces. These coatings will crosslink or self-crosslink and can beused in conjunction with other crosslinking agents such asmelamine-formaldehyde or urea-formaldehyde resins as well as phenolicresins, epoxy resins, isocyanates and blocked isocyanates. The Mannichadducts can also be used to crosslink with vinyl functionality as ispresent in resins such as diallylmelamine, butadiene, multifunctionalacrylic oligomers, unsaturated fatty acids in alkyd resins, fatty acidmodified epoxy resins, and the like.

Application of the treatment compositions of the present invention inthe treatment step to a metal or other desired surface can be carriedout by any conventional method. (While it is contemplated that the metalsurface will preferably be a conversion coated metal surface, thetreatment step can alternatively be carried out on an otherwiseuntreated metal surface to improve the corrosion resistance and paintadhesion thereof.)

For example, the treatment composition can be applied by spray coating,roller coating, or dipping. The temperature of the solution applied canvary over a wide range, but is preferably from 70° F. to 160° F. Afterapplication of the treatment solution to the metal surface, the surfacecan optionally be rinsed, although good results can be obtained withoutrinsing after treatment. Rinsing may be preferred for some end uses, forexample, in electrocoat paint application.

Optionally, the treated metal surface is dried. Drying can be carriedout by, for example, circulating air or oven drying. While roomtemperature drying can be employed, the use of elevated temperatures ispreferred to decrease the amount of drying time required.

After drying (if desired) the treated metal surface is then ready forpainting (with or without the Polymer Materials of the presentinvention) or the like. Suitable standard paint or other coatingapplication techniques such as brush painting, spray painting,electro-static coating, dipping, roller coating, as well aselectrocoating, may be employed. As a result of the treatment step ofthe present invention, the conversion coated surface has improved paintadhesion and corrosion resistance characteristics.

Further understanding of the present invention can be had from thefollowing illustrative examples. As used herein "salt spray" refers tosalt spray corrosion resistance measured in accordance withASTM-B117-61. As used herein, "Scotch Tape Adhesion" refers to the 180°T-bend adhesion test as described in ASTM-D3794-79. In summary, panelsare scribed in the center and subjected to the ASTM tests. The ratingtests for corrosion are measurements of the amount of "creeping" thepaint does from the scribe in units of 1/16 of an inch. The superscriptsrepresent the number of spots that are present.

EXAMPLE I

A polymer of the present invention is made as follows. A resin flask ischarged with 400 mls Propasol P (a propoxylated propane solvent obtainedfrom Union Carbide Corp., Danbury, Conn.) and 160 g Resin M (obtainedfrom Maruzen Oil MW=5000). A slurry of 263.3 g N-methyglucamine in 400deionized water is added, and the mixture is warmed to 60°-65° C. whilestirring. Next, 100.2 mls of 37% formaldehyde is added over one andone-half hours. The mixture is then warmed to 90° C. and held for sixhours. After cooling, the mixture is diluted to 9.6% solids withdeionized water. The pH of the final solution is 9.1 and the solutioncomprises an N-methyl-glucamine derivative.

Dilute solutions of the above formulation containing HF and/or H₂ TiF₆and sometimes Aerosil 200 are applied to bare aluminum metal as follows.In a typical aluminum treatment operation, aluminum panels are cleanedusing Parco* Cleaner 339 for 10 seconds at 155° F., rinsed for 10seconds with hot water, squeege dried, run through a roller-coatersqueegee containing the treatment solution, then flash dried in a 200°F. oven for 30 seconds. Treated panels are then painted with variouspaints and subjected to 504 hours acetic acid accelerated testing andcompared to B 722/Parcolene 10 controls. Test results are set forth inTables I-III. All percentages refer to percent solids in the respectivetreatment solution.

                  TABLE I                                                         ______________________________________                                        Accelerated Testing Results - DuPont Lucite 21000 Paint                                    Treatment                                                                    Solution         504 Hrs.                                         N-methyl-glucamine     Aerosil     Acetic Acid                                Derivative    H.sub.2 TiF.sub.6                                                                      200     pH  Salt Spray                                 ______________________________________                                        0.5%          --       --      3.2 N/N                                        0.5%          --       --      4.5 N/N                                        0.5%          0.1%     --      4.0 MD9/0-1.sup.s                              0.2%          --       --      4.5 N/Very Few                                 0.5%          --       0.5%    3.2 N/N                                        0.3%          --       0.7%    4.5 N/N                                        0.3%          0.1%     0.7%    3.0 N/N                                        2-(methylamino)ethanol                                                        Derivative                                                                    0.5%          --       --      3.2 D9/MD6 0-1.sup.s                           0.5%          0.1%     --      3.0 N/M6                                       diethanolamine                                                                Derivative                                                                    0.5%          --       --      3.2 0-2.sup.s /VF8 0-1.sup.s                   0.5%          0.1%     --      3.0 0-1.sup.s /N                               B 722/Parcolene 10                 N/N                                        Control                                                                       Clean only control                 D8/D4 0-3.sup.s                            ______________________________________                                    

                  TABLE II                                                        ______________________________________                                        Accelerated Testing Results - Glidden Polyure 602-W166 Paint                              Treatment                                                                     Solution         504 Hrs.                                         N-methyl-glucamine     Aerosil     Acetic Acid                                Derivative    H.sub.2 TiF.sub.6                                                                      200     pH  Salt Spray                                 ______________________________________                                        0.5%          --       --      4.5 N/N                                        0.5%          0.1%     --      4.0 N/F9                                       0.3%          0.1%     0.7%    3.0 N/N                                        0.2%          --       --      4.5 N/N                                        2-(methylamino)ethanol                                                        Derivative                                                                    0.5%          --       --      3.2 0.1.sup.s /VF.sup.4 0-3.sup.s              0.5%          0.1%     --      3.0 0.1.sup.s /VF6 0-2.sup.s                   dietholamine                                                                  Derivative                                                                    0.5%          --       --      3.2 n/0-1.sup.2s                               0.5%          0.1%     --      3.0 N/N                                        B 722/Parcolene 10                 N/N                                        Control                                                                       Clean only control                 0-2.sup.s /0-1.sup.2s                      ______________________________________                                    

                  TABLE III                                                       ______________________________________                                        Accelerated Testing Results - PPG-ILW-11704 Paint                                                              504 Hrs.                                     N-methyl-glucamine                                                                          Treatment Solution Acetic Acid                                  Derivative    H.sub.2 TiF.sub.6                                                                       pH       Salt Spray                                   ______________________________________                                        0.5%          --        3.2      N/N                                          0.5%          --        4.5      N/N                                          0.5%          0.1%      3.0      0-1.sup.s                                    2-(methylamino)ethanol                                                        Derivative                                                                    0.5%          --        3.2      0-1.sup.s /0-1.sup.s                         0.5%          0.1%      3.0      0-1.sup.s /0-1.sup.s                         diethanolamine                                                                Derivative                                                                    0.5%          --        3.2      0-1.sup.s /FM9 0-1.sup.s                     0.5%          0.1%      3.0      0-1.sup.s /VF9                               B 722/Parcolene 10               N/N                                          Control                                                                       Clean only control               0/1.sup.s VF6 0-2.sup.3s                     ______________________________________                                    

EXAMPLE II

In a typical steel treatment operation, the steel is initially cleanedby a mineral spirits wipe, followed by Parco* Cleaner 338 for 60 secondsat 160° F., hot water rinsed 30 seconds, 60 seconds B-1000 treatment at155° F., 30 seconds cold water rinse, and then post-treated with theN-methyl-glucamine derivative of Example I. Some of the panels wererinsed after post-treatment, others were not rinsed. All panels werethen baked in a 350° F. oven for 5 minutes. The treated panels werepainted with Duracron 200 paint. The paint was scribed, and the panelssubjected to salt spray accelerated testing for 504 hours, and comparedto Parcolene 95 and Parcolene 60 controls. Test results for twovariations are in Table IV.

                  TABLE IV                                                        ______________________________________                                                                     504 Hrs.                                         Post-Treatment  Conc./pH     Salt Spray                                       ______________________________________                                        Parcolene 60 Controls                                                                         -/4.3        N                                                2-(methylamino)ethanol                                                                        0.1%/6.3     0-2.sup.s                                        Derivative                                                                    Diethanolamine  0.1%/6.3     0-1                                              Derivative                                                                    Deionized Water -1-          4-5                                              N-methyl-glucamine                                                                            0.1%/7.9     0-1.sup.s                                        Derivative                                                                    N-methyl-glucamine                                                                            0.1%/6.3     0-1.sup.2s                                       Derivative                                                                    Metylbutylamine 0.1%/6.3     1-1.sup.2s                                       Derivative                                                                    ______________________________________                                    

EXAMPLE III

Into a one (1) liter reactor equipped with a reflux condensor, nitrogensparge, thermocouple, and addition funnel was added 450 ml of butylcellosolve (Union Carbide). To the solvent over a 90 minute period wasslowly added 180 grams of poly-4-vinylphenol powder (MW=5,000) with goodagitation. The temperature was then increased to 100° C. to dissolve anyresin from the walls of the flask and then 89.25 grams of Araldite DY025, a mono-functional epoxide was added followed by the addition of one(1) gram of N,N-Dimethylbenzylamine. The temperature was graduallyincreased and the reaction mildly exothermed to 167° C. The reaction waspost-heated at 175°-185° C. for an additional 3 hours and then cooled.The final solids of the reaction was 40.3% (baked at 350° C. for 15minutes) indicating a 99% completion of the reaction.

The epoxide modified poly-4-vinylphenol derivative from above was usedin the preparation of a Mannich derivative as cutlined below. To theabove reaction was added 90.13 grams of 2-(N-methylamino)-ethanol andthe reaction heated to 50° C. Over a 45 minute period 97.4 grams of a37% formaldehyde solution was then added and then the reaction waspost-heated for the first 2 hours at 50° C. and then 3 hours at 80° C.The reaction was found to be complete by titration for residualformaldehyde.

A portion of the above solution was adjusted to a pH of 6.5 withphosphoric acid and diluted to 17% solids with deionized water. Zincphosphated cold rolled steel panels (Bonderite Ep-1) were dipped intothe diluted solution of the above polymer and a DC current applied tothe panel where the panel was made the cathode and a 316 stainless steelpanel was made the anode. The panels were withdrawn from the treatmentbath, rinsed with deionized water and oven baked at 400° F. for 20minutes. A coating weight of approximately 0.5 mils was attained. Whentested by treatment with Methyl ethyl ketone and simultaneously rubbedwith a cloth, solvent resistance of over 100 rubs was demonstrated.

The above polymer solution in water was also cast on a zinc phosphatedcold rolled steel panel by the use of a draw-down bar and then baked at400° C. for 20 minutes. Again over 100 MEK rubs resulted after the ovenbake, while without an oven curing step only 1 to 3 MEK rubs wereobtained. The results indicate that the Mannich derivative of thepolymer above is self-crosslinking and can be used to form a coating ona metal surface by either casting a film or by cathodicelectrodeposition. Good solvent resistance can be attained without theaddition of external crosslinking agents although added externalcrosslinking agents are not expressly excluded.

EXAMPLE IV

A Mannich adduct of poly-4-vinylphenol with N,N-diallylamine wasprepared as above by reacting the following ingredients.

1. 131.2 grams 30.5% poly-4-vinylphenol in Proposal P (Union Carbide)

2. 27.5 grams of Propasol P

3. 33.4 grams of N,N-diallylamine (Aldrich Chemical CO)

4. 26.4 grams of 37.9% formaldehyde solution.

The ingredients were mixed and reacted first for five hours at 50° C.and then 2 hours at 80° C. The reaction was followed by thedisappearance of formaldehyde and the reaction stopped when 99%complete.

EVALUATION OF SELF-CROSSLINKING REACTION

The reaction mixture of poly-4-vinylphenol, diallylamine andformaldehyde from above was diluted to 17.5% solids and cast on acleaned aluminum panel (#3003 alloy). A wet film weight of 3 mils and adry film weight of approx. 1 mil was attained. The bake conditions were350° C. for ten minutes. MEK (methyl ethyl ketone) solvent resistance of500+ double rubs using automated test equipment was obtained.

The above diallylamine Mannich adduct of poly-4-vinylphenol was mixed inapproximately 10 parts Mannich to 12 parts Monsanto RJ-101 resin (astryene-allyl alcohol copolymer). This polymeric coating formulation wascast on an aluminum panel using a draw down bar and baked in aconvection oven at 350° F. for 10 minutes. The cured coating did notfail even after 500+ MEK double rubs.

A coating cast from only the Monsanto RJ-101 polymer failed inapproximately 8-10 MEK rubs. The above results indicate that the Mannichderivatives of polyvinylphenols are excellent crosslinking agents forpolymeric systems or can be used as polymeric coatings possessingself-crosslinking properties.

EXAMPLE V

80 grams of a poly-4-vinylphenol-methyl methacrylate copolymer fromMaruzen Oil Co. of U.S.A. Inc., New York, N.Y. (Mw=14,090 and Mn 6,800PVP/MMA ratio=57/43 by weight) is dissolved in 160 mls of propasol p in160 mls of deionized water. 29.2 mls (0.36 equivs) of 99%methylethanolamine is added, followed by 160 mls deionized water. Themixture is brought to 40°-50° C., then 29.3 grams of a 37% solution offormaldehyde are added (0.36 equivalents) dropwise over a one hourperiod while maintaining the reaction at 40°-50° C. The mixture is thenwarmed to 80° C. and maintained at this temperature for four (4) hours.After cooling to ambient temperature, 56.7 grams of a 30% hydrogenperoxide solution is added and allowed to stir overnight at 35° C. Theabove solution is then neutralized to a pH of 6 and diluted to 15%solids by the addition of 517 mls of deionized water. By the synthesisof the amine oxide of the Mannich adduct, much less acid is needed toproduce a water soluble polymer.

What is claimed is:
 1. A polymer compound comprising:a copolymermaterial wherein at least one portion of said co-polymer has thestructure: ##STR6## wherein y₄ is: ##STR7## R₁₀ is a hydroxy-alkylsubstituent resulting from the reduction of an imine generated by thecondensation of an amine and an aldose, ketose or mixture thereof; andat least a fraction of said portion is polymerized with acrylonitrile.2. A composition comprising (a) a polymer compound according to claim 1and (b) a surface treatment carrier having (a) dissolved or dispersedtherein.
 3. A composition according to claim 2 wherein the carriercomprises water.
 4. A composition according to claim 2 wherein thecarrier is aqueous and the polymer has been neutralized with an acid. 5.A composition according to claim 4 wherein the acid is carbonic acid. 6.A composition according to claim 4 having a pH of from about 0.5 toabout
 14. 7. A composition according to claim 6 having a pH of fromabout 2.0 to about
 12. 8. A composition according to claim 2 whereinsaid polymer compound comprises about 0.001 to about 80% by weight ofthe final composition.
 9. A composition according to claim 8 whereinsaid polymer compound comprises from about 0.001% to about 10% of saidcomposition.
 10. A composition according to claim 9 wherein said polymercompound comprises from about 0.001 to about 5% of said composition. 11.A composition according to claim 10 wherein said polymer compoundcomprises from about 0.025% to about 1% of said composition.
 12. Acomposition according to claim 8 wherein said polymer compound comprisesfrom about 1% to about 80% of said composition.
 13. A compositionaccording to claim 6 which additionally comprises a complex fluoridematerial.
 14. A composition according to claim 2 which additionallycomprises a dissolved or dispersed compound that includes compounds oftitanium, zirconium, hafnium, silicon, or mixtures thereof.
 15. Acomposition according to claim 2 which additionally comprises an oxideof silicon, titanium, tin, aluminum, cobalt, nickel, or mixturesthereof.
 16. A composition according to claim 2 which additionallycomprises a paint system additive selected from the group consisting ofa film forming resin, a pigment, a binder, particulate zinc, or mixturesthereof.
 17. The polymer of claim 1 wherein said polymer is condensedwith a second compound selected from the group consisting of phenols,tannins, novalak resins, lignin compounds, together with aldehydes,ketones or mixtures thereof, to produce a condensation resin product,said condensation resin product then being further reacted by theaddition of "Z" to at least a portion of it by reacting said resinproduct with (1) an aldehyde or ketone and (2) a secondary amineproducing a final adduct which can react with an acid.
 18. A compositionaccording to claim 17 wherein said second compound is selected from thegroup consisting of phenol, alkylphenol, arylphenol, cresol, resorcinol,catechol, pyrogallol, and mixtures thereof.